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14 The Geochemical News

Bubbles in Amsterdam
melt and fluid inclusion research
at the Vrije Universiteit

When Jacques Touret, professor of petrology, mineralogy


and ore geology, was about to retire from the Vrije
Universiteit, my alma mater, I asked around for a
contribution about his research. Jacques responded by
asking me to drop by. “Why don’t you write it?” suggested
Jacques and he introduced me to his colleague Igor
Nikogosian. Igor then introduced me to melt inclusions.
Fluid inclusions

On March 29, 2001, the University of Liège in Belgium awarded and have taken their expertise to many countries: Germany (Fons
an honorary doctorate (Docteur Honoris Causa) to Jacques van den Kerkhof), Italy (Maria Luce Frezotti), South Africa (Jan
Touret. On September 19, 2001, the VU organized a symposium Marten Huizenga), China (Bin Fu and Cong Yuexiang) and soon
in Jacques’s honor: Fluids at depth. In addition, the journal Lithos Chili (Eduardo Campos). Other Ph.D. students have also spread
dedicated an entire issue to Jacques. Jacques Touret, having the news about Amsterdam, for instance in Indonesia (Jan
reached the Dutch retirement age, was leaving. He has bought Sopaheluwakan) and Zimbabwe (Hielke Jelsma, now in South
a house in France and moved back to his home country, where Africa).
his wife works as a mineralogist and curator at the Musée de
Mines of the École des Mines in Paris. After the recent graduation Ernst Burke - the Belgian mineralogist, Raman probe specialist
of Bin Fu, Jacques still has one Ph.D. student left in Amsterdam and head of the Microanalysis lab at the VU earth science
(Eduardo Campos). Jacques Touret is also a member of the Royal department - and his coworker Wim Lustenhouwer must be
Netherlands Academy of Sciences and as such is currently mentioned as well in this respect. Their role was and continues
concerned with documenting the history of the earth sciences. to be essential. Ernst, Wim and their colleagues enable top-notch
So instead of traveling back and forth to France, he now travels quality analysis of inclusions.
back and forth to The Netherlands, where he will always be very
welcome. The Dutch like Jacques, not only because of his Brief history of fluid inclusion research
scientific contributions but also because of his friendly nature.
Jacques is well known for his appreciation of the finer things in Fluid inclusions were already recognized at the beginning of the
life, his enthusiasm, his French charm, and his sense of humor. eighteenth century and later became a regular part of
petrography. H. Vogelsang - professor of petrology at the
Fluid inclusion research at the VU University of Delft more than a century ago - demonstrated that
fluids found in granitic minerals such as beryl, topaz and quartz,
Jacques Touret joined the Vrije Universiteit in 1980, as a full were in fact supercritical CO2. During the first half of the twentieth
professor in petrology, mineralogy and ore geology, freshly century, interest in fluid inclusions waned. Only scientists in the
imported from France. He quickly established a fluid inclusion former Soviet Union continued to study them and later became
research lab, which became a reference for this type of research. a source of expertise for the west.
Jacques’s fluid inclusions students came from many countries
Fluid inclusion research initially was largely - but not solely - the
domain of metamorphic petrology. Certain high-grade
A melt inclusion metamorphic rocks that were initially considered rare oddities
turned out to be important components of the continental crust.
These rocks are called granulites. In the 1970’s, granulites were
discovered to contain many CO2-rich fluid inclusions and this
spawned renewed interest in the topic. Granulites are one of
Jacques Touret’s favorite research topics and that was his angle
for studying fluid inclusions.

They are tiny cavities in crystals and can contain three phases
(solid, liquid and gas). Fluid inclusions in igneous rocks may
represent the volatile phase of a magma. Fluid inclusion research
entails the use of a heating-freezing stage with which
homogenization temperatures can be determined. The Raman
probe is another prominent player in fluid inclusion research: it’s
an often-used analytical tool. Vital in the work on fluid inclusions
is the assumption that the inclusions have not leaked any of their
contents. (See also Touret, 2001.) It may come as a surprise to

Newsletter of the Geochemical Society


Number 112, July 2002 15
earth scientists in other subdisciplines that fluids at depth (H2O, Petrology contains material that was presented at that
CO2, CH4, N2, He) may well exceed by many orders of magnitude symposium.
the mass of fluids contained in the outer layers of the terrestrial
system. Melt inclusion research at the VU

The original fluid inclusion research now appears to be overtaken About four years ago, Jacques Touret decided to install melt
by one of its categories: melt inclusions. GeoRef turned up 73 inclusion facilities at the VU. “Jacques was always telling me
results for “melt inclusions” in publications between 1985 and that most petrologists were missing half the excitement by not
1970, 52 for publications between 1985 and 1990 and the number looking at inclusions”, writes Tim Elliott who used to work in
has been rapidly increasing since. The 1995 AGU Spring Meeting Amsterdam but is now at Bristol. Jacques then contacted Alex
included a session called “Melt inclusions and petrogenetic Sobolev who proposed that Igor Nikogosian help him set up the
indicators in igneous environments”. Vol. 4, No. 3 of the journal equipment and methods. The VU already had a Linkam stage
for melt inclusion work, but it did not allow quenching to glass at
equilibrium conditions. Igor came to Amsterdam and set up the
stage, with the help of Ernst Burke and particularly his colleague
Wim Lustenhouwer. Of course, Igor did not just come to
Amsterdam to install the stage. He set up the entire methodology
and has been actively boosting melt inclusion research since,
particularly by his own contributions to the field.

Brief history of melt inclusion research

The history of melt inclusion research resembles that of fluid


inclusions in general. Melt inclusions had already been noticed
in the eighteenth century, but in the 1970’s, only Sobolev’s group
in the Soviet Union and a few other groups (in Japan, China and
the DDR) were actually studying them. It was the Russian group
that created a crucial breakthrough: the development of the
Vernadsky stage. The Vernadsky stage not only enabled heating
to high temperatures, but also rapid quenching. Igor Nikogosian
was part of Sobolev’s group of Ph.D. students in the former Soviet
Union. These Russian students have all swarmed out to the west,
just as Touret’s former fluid inclusion students did. Andrey
Gurenko used to work at the GEOMAR research center in Kiel,
but has recently moved to Potsdam where he joined Ilya Veksler.
Maxim Portnyagin is now in Kiel. Vadim Kamenetsky and Leonid
Danyushevsky are both working at the University of Tasmania in
Australia. In 2001, the Alexander von Humboldt Foundation gave
a Wolfgang Paul Award to Alex Sobolev, then at the Vernadsky
Institute of Geochemistry and Analytical Chemistry in the Russian
Federation. As a Humboldt awardee, he currently works in Mainz,
Germany. While fluid inclusion research appears to have been
the domain of metamorphic petrology (not exclusively!), melt
inclusions are particularly impacting igneous petrology. Simplified,
one could say that petrologists study all aspects of a rock and
then try to say what exactly made the rock into what it is now.
While this may sound trivial, this kind of information forms the
pieces of a puzzle. The assembled puzzle would show the
workings and details of the system know as the solid earth, and
of part of the hydrosphere and atmosphere as well.

What are melt inclusions and why are they special?

Melt inclusions are tiny blobs of magma trapped within crystals


(phenocrysts). At room temperature, they are solid (unlike
“regular” fluid inclusions). Their typical size is 1 to 50 µm but
they can be considerably larger as well. They can be completely
glass, partly glass and partly crystalline, or wholly crystalline.
Glassy melt inclusions may contain a shrinkage bubble. Primary
This is what happens to a melt inclusion as it cools.
melt inclusions are the most important as they contain the magma
The reverse happens on a heating stage during a in which the crystal formed. Secondary melt inclusions form after
microthermometric run. Courtesy Igor Nikogosian. crystallization of the host mineral and are less important, but

Newsletter of the Geochemical Society


16 The Geochemical News
can for instance yield important insights in the nature of
metasomatic fluids (see Schiano et al., 1994).

What is so special about melt inclusions is that, ideally, they


constitute a time machine. They allow us to look back in time.
The processes that (metamorphic and) igneous petrologists study
tend to wipe out each other’s results. Any rocks we see at the
surface of the earth have been subjected to a wide range of
processes. All we see is end products. We would like to know
how they started out. Were they originally part of one magma in
a magma chamber or are they the result of the mixing of several
magmas? Did they melt again at some point and assimilate other
rocks at that point? Did they assimilate other rocks before they
first crystallized? Have they been recycled through the big magma
machine and have parts of them been exposed to atmospheric
conditions before? Often, we don’t know. All we know is that most
rocks have come a long way.

Jacques Touret and fluid


inclusions. Courtesy
Frank Beunk. Rare earth element compositions of melt inclusions in oli-
vine from Hawaiian tholeiites, including range of whole-
rock data. These data are not only normalized to chon-
drites but also to 10 wt.% Al2O3 of primary melt from
Sobolev and Nikogosian (1994). These ultra-depleted
(UEM) and ultra-enriched (UDM) melt components were
completely unknown until they were found in these inclu-
sions trapped in high-Mg olivines. This indicates the co-
existence of very different magmas in an efficiently mixing
magma conduit.

crystal defects (energetically favorable). These are, of course,


also sites of potential diffusion routes. The degree to which a
melt inclusion was closed or not is linked to element
concentrations, concentration gradients and diffusion coefficients.
The larger the chemical contrast between melt and host mineral,
the better the isolation (Sobolev, 1996). Danyushevsky et al.
(2002) recently outlined some of the complications of melt
Melt inclusions, ideally, are tiny samples taken along that road. inclusion research. Nielsen and coworkers described earlier how
They allow petrologists to travel back in time vicariously and take to check the integrity of melt inclusions (1998).
a snapshot of physicochemical conditions of certain points along
that path. It won’t get any better than that because humans do Methodology
not live long enough and can’t survive high temperatures and
high pressures. Humans cannot jump into a subduction zone As indicated earlier, the high-temperature heating/quenching
and witness these processes firsthand, but melt inclusions make stage is paramount in this work. First, phenocrysts with melt
good proxies. High-PT experiments are the only other thing that inclusions are selected and separated from the rock, mounted in
comes close. If you do an ‘old-fashioned” whole-rock analysis, epoxy and polished. Second, if the inclusions are fully vitreous,
you get the chemical result of a series of processes. With the composition of the glass can be determined without any
supplementation from other data, such as mineral analyses and problems. If the inclusions are partly of wholly crystalline, the
geothermobarometry, you hope to be able to reconstruct at least inclusion first needs to be melted and then quenched (to prevent
some of the rock’s history. By using data from melt inclusions in crystal formation), after which the glass can be analyzed. High-
phenocrysts you may end up with a complete PTt (pressure- temperature microthermometry - the heating/quenching stage -
temperature-time) trajectory and a very good idea of the allows the petrologist to determine the equilibrium conditions and
processes along that trajectory. Melt inclusions are magmatic crystallization temperatures for the inclusion and its host. Briefly,
information agents. the inclusion is heated in a pure He atmosphere until it melts.
Kinetic experiments - basically consisting of a series of
Does it always work this way in practice? Of course not. The thermometric runs in which the heating rate is varied and the
ideal scenario is based on the assumption that the melt inclusion inclusion carefully observed under the microscope - are carried
is a chemically closed system and has been since the time of out to determine the best conditions. The run is the reverse of
entrapment. Melt inclusions tend to become trapped at sites of the natural cooling process: the phases in the inclusion disappear

Newsletter of the Geochemical Society


Number 112, July 2002 17
one by one until the contents of the inclusion are completely Igor Nikogosian.”“Especially for Si, Ca, Al, Ti and Na. It is difficult
homogenized. Without visual control, one can only guess what to make corrections for those.” During these experiments, the
happens in the inclusion and may well end up with false results. host crystal may influence the inclusion, while originally, it was
It would, for instance, be impossible to quench at the right the magma that determined the host mineral. Pressure effects
moment, without visual control. can also play a role: the host mineral is not at its original pressure.
That is why it is also very important to rapidly quench a melt
EPMA, LA-ICP-MS, FTIR spectroscopy, ion probes for trace inclusion once it has homogenized. See also Danyushevsky et
elements and H2O, and SYXRF are some of the analytical tools al. (2002).
used in melt inclusion research. The microbeam developments
lifted melt inclusion research out of its cradle after the In addition, melt inclusion work can be very painstaking. What
development of the Vernadsky stage. The analytical data can be you hope to find are so-called exotic inclusions: the ones that
fed into mathematical models and the results of the have retained very deep parent magmas. No more than about
microthermometric runs can then be compared to the calculated 5% of all the melt inclusions in a rock are exotic. You may end up
data. studying literally hundreds and hundreds of inclusions before you
strike pay dirt. The rewards are worth the effort: you may find
However, working with melt inclusions is not as easy at it may that the rock you have is not the result of the mixing of three but
initially sound. If you heat inclusions too slowly, re-equilibration of five magmas. It is the nature of those magmas that reveals a
at conditions not representative of trapping will occur. If you heat great deal of information about the processes in the deep earth.
inclusions too rapidly, the actual conditions in the inclusion are
those of a lower temperature. Overheating (above Examples of melt inclusion work
homogenization) is not necessarily a problem as long as you
immediately quench the inclusion. “But if you overheat a Melt inclusions enable determination of the oxygen fugacity at
clinopyroxene host by 25 to 50 degrees, you end up with a the time of magma crystallization, on the basis of the Fe2+/Fe3+
completely different composition of the melt inclusion”, warns ratio in spinel and the composition of the associated olivine (see
Danyushevsky and Sobolev, 1996).

A Much work has focused on volcanic


rocks such as those of Mount Shasta
and in Italy and particularly on
intraplate magmatism, such as of
Hawaii. It is widely accepted that
mantle plumes contain recycled
oceanic crust. Melt inclusions contain
the information to prove this (Sobolev
et al., 2000).

A recent development is the


determination of the isotope
composition in melt inclusions. (See
Sobolev, 1996.) Some researchers
have, for instance, used 40Ar/39Ar data
B C from melt inclusions in quartz to
determine residence time scales of
silicic magma chambers, but there are
some complications related to the
question whether these inclusions can
be regarded as a closed system with
respect to 40Ar (Winick et al, 2001).
Will isotope work on melt inclusions
refute earlier findings? “While
determining isotope compositions of
melt inclusions will not dramatically
A. General view of the Vernadsky-Institute type high-temperature upset earlier findings, I do expect it to
set-up with controlled He atmosphere and video display at the VU. reveal new knowledge about the
isotope systems”, replies Igor
B. Detail of the high-temperature heating stage at the VU (up to Nikogosian.
1500 degrees C).
Boron - isotope composition - in melt
C. General view of the heating/quenching element of the Vernadsky inclusions is a good tracer for a crustal
stage at the VU; arrow indicates the position of the melt inclusion. component diluted with mantle
material and indicates that arc
The quenching time is 1-2 seconds.
magmas also contain an oceanic crust

Newsletter of the Geochemical Society


18 The Geochemical News
component (Rose et al., 2001; Gurenko and Chaussidon, 1997). melt inclusions can preserve their original trace element
concentrations over time, the same cannot be said of some
A spin-off from the work with the Vernadsky stage is that it also elements in plagioclase-hosted inclusions.
enables new fluid inclusion work. Previous fluid inclusion work

LEFT: Jacques Touret during the


ceremony in Liège (front row, third
person on the left). Seated on the
far right, front row, is His Majesty
King Albert II of Belgium. Courtesy
Pascale Scarpa. Copyright TILT
PHOTOGRAPHY LIÈGE - www.tilt-
photographie.be.

BELOW: Jacques Touret receives


the honorary doctorate from the
Université de Liège (March 29,
2001). Courtesy Pascale Scarpa.
Copyright TILT PHOTOGRAPHY
LIÈGE - www.tilt-photographie.be.

did not involve heating to over 500 degrees


C. Now with the Vernadsky stage, fluid
inclusions can also be taken to much higher
temperatures that may be much closer to
their formation conditions (see Campos et
al., 2002).

Other geoscientists about melt


inclusions

Of course, Jacques Touret and Igor


Nikogosian are not the only petrologists
dedicated to inclusion research. Rumor has
it that Dan McKenzie became obsessed with
them and that Al Hofmann is also a real
convert. So what do you hear if you ask
around?

Liz Cottrell is a Fulbright Scholar working on


her Ph.D. at Lamont, where she now studies
core formation as an experimentalist with
David Walker. Liz has used melt inclusions in her research and Based on the study by Cottrell et al. (2002), there are several
attended a melt inclusion workshop in Grenoble in March of 2000 ways in which the melt inclusion community could improve the
(cosponsored by Elsevier Science). She writes: quality of both the data and the interpretations of melt inclusions.
Every effort should be made to gather data from a variety of
”While melt inclusions provide one unique tool for understanding phenocryst types from the same location. The partitioning of trace
petrogenesis, it is easy to misinterpret the data they provide by elements varies among crystal hosts, so looking at inclusions in
failing to take into account diffusional processes. Exciting new more than one type of phenocryst might unravel any diffusional
work focuses on the trace element contents of melt inclusions. overprinting of the original concentrations. If only one host type
However, some trace elements may diffuse rapidly enough to is available, then it is especially important to look at the statistical
obscure the original information content of the melt inclusions. distribution of trace element concentrations in order to spot the
We tried to quantify this in Cottrell et al. (2002) by demonstrating potential effects of diffusion. I believe there is also an untapped
that diffusion will have different but predictable effects in different wealth of information in the trace element zoning around melt
host phases. For example, while it appears that olivine-hosted inclusions. With the proper microanalytical work, trace element

Newsletter of the Geochemical Society


Number 112, July 2002 19
zoning in the crystal surrounding the melt could provide environments, such as mid ocean ridges, island arc volcanoes
information about the timing and evolution of inclusion and so on. In many cases our understanding of geochemical
compositions. processes is largely based on variations between various
geochemical components, so something that can help us image
The bottom line is that melt inclusion work has an exciting future, these differences in much greater detail is of tremendous value.
but care needs to be taken to unravel the modifications caused
by diffusion. This can best be accomplished if high quality trace Although there are still questions regarding the processes that
element data are collected from melt inclusions from multiple trap and subsequently modify inclusions, advances in analytical
hosts from one location and the information compared to model techniques promise to provide even more insight in the future. In
predictions. In this manner, post entrapment diffusion can be particular, and in contrast to Igor, I think that development and
quantified and subtracted so that the real information about wide application of techniques for isotopic analyses of melt
primary liquids can be elucidated.” inclusions will produce important results (and in fact they already
have), allowing us to see through melting-related processes and
Danyushevsky et al. (2002) appear to concur with Liz. They also take a fresh look at the nature of the mantle and crustal rocks
argue that many articles pay a great deal of attention to from which magmas ultimately derive.”
interpreting the composition of inclusions, whereas there is little
regard for the processes that affect inclusions after trapping. Future of the inclusion group at the VU

Roger Nielsen (Oregon State): “First and foremost - we as Amsterdam is one of the few places in the world with a fully
petrologists need to get past the prejudice that melt inclusions operational Vernadsky stage. Vernadsky stages are also up and
are “secondary” sources of petrologic information relative to running in Australia (Hobart), Norway (Oslo), and France (Saclay).
sources we are more familiar with such as bulk rock or lava Vernadsky stages have been, are being, or will be installed shortly
chemistry. The data obtained from melt inclusions have their own in Italy (Siena), the US (Woods Hole and Blacksburg), and
set of interpretive criteria quite apart from “normal” data. However, Germany (Mainz and Kiel).
that does not mean that they are inferior in any way. We will gain
our greatest leverage when we can fully integrate all data types. The Amsterdam group is involved in many international
That will require us to abandon hearsay criticism of melt inclusion cooperations and always has been. It is currently rapidly turning
data and obtain reliable, reproducible experimental constraints out papers based on melt inclusion work. A recent issue of
on the important processes that can effect the composition of Chemical Geology focused completely on melt inclusions and
trapped melts.” contains the results of the Grenoble workshop. Three papers in
that issue are based on work conducted at the VU. A recent issue
Roger agrees that melt inclusions are essentially the only way to of Tectonophysics also contained a contribution from the VU melt
obtain data from earlier stages in the differentiation of a volcanic inclusion group. However, these are only a few examples. The
suite. “This is particularly true with regards to volatiles.” He group certainly has proved its right to exist and the search for
cautions: “When interpreting inclusion data, or any small scale Jacques’s successor has started.
geochemical data such as zoning, we must remember that the
scale of the features we are measuring are 8-10 orders of A factor that will play a huge role in the future developments at
magnitude smaller than the environments we are using the data the VU is whether the VU will continue to attract enough earth
to interpret.” science students. As in many other countries, this is becoming a
problem in The Netherlands. The recent number of applications
Tim Elliott (University of Bristol, U.K.) is also highly enthusiastic to the Dutch earth science Master’s programs shows a drop of
and emphasizes that he’s certainly not the only one. “The fantastic 40 percent (that also happened, for instance, to chemistry). In
range in compositions you see in individual olivine crystals that light, it is interesting to hear what Liz Cottrell writes about
(Sobolev et al., 2000) blew everyone’s mind. This put some her own career: “My decision to become an earth scientist stems
bewildering constraints on melting and mixing processes. I from the many wonderful mentors I’ve had in the field. They have
believe that Marc Spiegelman has recently come up with a model offered me guidance, encouragement, and funding.” This
that at last can explain some of this in a reasonably physically demonstrates the importance of individual earth scientists. They
plausible manner.” According to Tim, melt inclusion research is can and must inspire students, so that there continue to be
revolutionizing the understanding of melting and volatile budgets opportunities for excellent young scientists - like Liz Cottrell -
in subduction zones. “For this, the heating stage does not come who can take over in the future. It’s not just matters like the
into its own as self-quenched inclusions are best. But, such glassy number of high-quality publications and the amount of acquired
inclusion provide a record of pre-eruptive volatile contents that funding, which make a great scientist. It includes the integrity,
can’t be obtained in any other way.” Tim emphasizes that he enthusiasm and power to attract, inspire and keep good people.
admires Igor and considers him a great scientist: working very
hard, very skilled and also quite successful at forging international
collaborations. Angelina Souren
Associate Editor for The Geochemical News
Adam Kent (Dansk Lithosfærecenter, Copenhagen, Denmark) Angie@smarterscience.com
adds: “I think that the really exciting thing about melt inclusions
is that they are making geochemists and petrologists think about
the processes that produce igneous rocks in new ways -
principally because inclusions provide a record of the tremendous
diversity of magma compositions that occur in different igneous

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